The effect of ZrO 2 calcination temperature on its structure and acid-base characteristics was investigated to elucidate their relation to catalytic behaviour in methanol carboxylation. Varying the calcination temperature causes changes in ZrO 2 phase composition and acid-base characteristics. The base properties of ZrO 2 play a prominent role in dimethyl carbonate synthesis. Strong base sites (E CO2 > 78 kJ/mol) are needed to activate СО 2 . Tetragonal modification of zirconium dioxide has a higher basicity than the monoclinic. Thus, the greater the contribution of t-ZrO 2 in the catalyst, the greater its ability to activate СО 2 and therefore result in higher catalytic activity for methanol carboxylation. DMC selectivity was determined by the ratio of catalyst base site to acid site concentration.
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